KR20220093314A - 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide decision of - Google Patents

Abstract

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide In the powder X-ray diffraction by Cu-Kα ray, at least one crystal selected from the group consisting of a Ra1 crystal, Ra2 crystal, and Ra3 crystal each having a diffraction peak described in the specification.

Description

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide decision of

The present invention is 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)- It relates to a novel crystal of 1H-pyrazole-4-carboxamide.

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide (hereinafter referred to as compound A) is a crystal having a melting point of 131 to 134°C, and it is reported that it has a control effect against plant diseases (Patent Document 1).

WO 92/12970

An object of the present invention is to provide a novel crystal having physical properties different from those of the known crystal described in Patent Document 1 (hereinafter referred to as Ra4 crystal) and having more excellent plant disease control effect. .

The present inventors have discovered three novel crystals of Compound A (Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals), which have an excellent control effect against plant diseases.

That is, this invention is as follows.

[1] 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4- In the carboxamide,

2θ = 7.1 ± 0.2 °, 8.6 ± 0.2 °, 8.9 ± 0.2 °, 9.1 ± 0.2 °, 13.3 ± 0.2 °, 14.0 ± 0.2 °, 14.3 ± 0.2 °, in powder X-ray diffraction by Cu-Kα ray Form Ra1 crystals having diffraction peaks at 14.8 ± 0.2°, 16.0 ± 0.2°, 16.4 ± 0.2°, 20.3 ± 0.2°, and 20.6 ± 0.2°;

2θ = 4.3 ± 0.2 °, 8.5 ± 0.2 °, 10.8 ± 0.2 °, 11.4 ± 0.2 °, 12.4 ± 0.2 °, 12.8 ± 0.2 °, 15.1 ± 0.2 ° in powder X-ray diffraction by Cu-Kα ray Form Ra2 crystals having diffraction peaks at 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2°, and

2θ = 3.6 ± 0.2 °, 7.1 ± 0.2 °, 7.4 ± 0.2 °, 9.6 ± 0.2 °, 11.9 ± 0.2 °, 12.5 ± 0.2 °, 12.9 ± 0.2 °, in powder X-ray diffraction by Cu-Kα ray Ra3-form crystals with diffraction peaks at 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2°

At least one crystal selected from the group consisting of.

[2] 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)- as described in [1] For 1H-pyrazole-4-carboxamide, 2θ = 7.1 ± 0.2 °, 8.6 ± 0.2 °, 8.9 ± 0.2 °, 9.1 ± 0.2 °, 13.3 ± in powder X-ray diffraction by Cu-Kα ray Form Ra1 crystals with diffraction peaks at 0.2°, 14.0 ± 0.2°, 14.3 ± 0.2°, 14.8 ± 0.2°, 16.0 ± 0.2°, 16.4 ± 0.2°, 20.3 ± 0.2°, and 20.6 ± 0.2°.

[3] 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)- as described in [1] In 1H-pyrazole-4-carboxamide, 2θ = 4.3 ± 0.2 °, 8.5 ± 0.2 °, 10.8 ± 0.2 °, 11.4 ± 0.2 °, 12.4 ± in powder X-ray diffraction by Cu-Kα ray Form Ra2 crystals with diffraction peaks at 0.2°, 12.8 ± 0.2°, 15.1 ± 0.2°, 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2°.

[4] 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)- as described in [1] In 1H-pyrazole-4-carboxamide, 2θ = 3.6 ± 0.2 °, 7.1 ± 0.2 °, 7.4 ± 0.2 °, 9.6 ± 0.2 °, 11.9 ± in powder X-ray diffraction by Cu-Kα ray Form Ra3 crystals having diffraction peaks at 0.2°, 12.5 ± 0.2°, 12.9 ± 0.2°, 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2°.

[5] A plant disease control composition comprising one or more crystals according to any one of [1] to [4].

[6] A method for controlling a plant disease, comprising treating a plant or soil in which the plant grows in an effective amount of one or more crystals according to any one of [1] to [4].

[7] Use of one or more crystals according to any one of [1] to [4] for controlling a plant disease.

[8] at least one component selected from the group consisting of group (a), group (b), group (c) and group (d), and at least one crystal according to any one of [1] to [4] Compositions containing:

Group (a): the group consisting of insecticidal active ingredients, acaricidal active ingredients and nematicidal active ingredients;

Group (b): bactericidal active ingredients;

Group (c): plant growth modulating components;

Group (d): repellent components.

[9] A seed or vegetative reproductive organ containing an effective amount of the crystal according to any one of [1] to [4] or an effective amount of the composition according to [7].

The present invention provides three types of novel crystals (Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals) of Compound A exhibiting a control effect against diseases of plants. These crystals show a better control effect on plant diseases than the known Ra4 type crystals.

1 is a diagram showing a powder X-ray diffraction pattern of Ra1-type crystals. The vertical axis indicates the diffraction intensity (unit: cps), and the horizontal axis indicates the diffraction angle 2θ (unit: °).
Fig. 2 is a diagram showing a powder X-ray diffraction pattern of Ra2-type crystals. The vertical axis indicates the diffraction intensity (unit: cps), and the horizontal axis indicates the diffraction angle 2θ (unit: °).
Fig. 3 is a diagram showing a powder X-ray diffraction pattern of Ra3-type crystals. The vertical axis indicates the diffraction intensity (unit: cps), and the horizontal axis indicates the diffraction angle 2θ (unit: °).
Fig. 4 is a diagram showing a powder X-ray diffraction pattern of a Ra4 crystal. The vertical axis indicates the diffraction intensity (unit: cps), and the horizontal axis indicates the diffraction angle 2θ (unit: °).
Fig. 5 is a diagram showing molecular packing in the crystal lattice of the Ra1-type crystal.
Fig. 6 is a diagram showing molecular packing in the crystal lattice of the Ra2-type crystal.
Fig. 7 is a diagram showing molecular packing in the crystal lattice of the Ra3-type crystal.
Fig. 8 is a diagram showing a differential scanning calorimetry (DSC) curve of an Ra1 crystal. The vertical axis indicates heat flow (unit: W/g), and the horizontal axis indicates temperature (unit: °C).
Fig. 9 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra2 crystal.
Fig. 10 is a diagram showing a differential scanning calorimetry (DSC) curve of the Ra3-form crystal.
11 is a diagram showing a differential scanning calorimetry (DSC) curve of a Ra4 crystal.
12 is a diagram showing a spectrum diagram of an infrared spectrum of an Ra1 crystal. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of irradiated infrared rays.
Fig. 13 is a diagram showing a spectrum diagram of an infrared spectrum of a Ra2 crystal. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of irradiated infrared rays.
Fig. 14 is a diagram showing a spectrum diagram of an infrared spectrum of an Ra3-type crystal. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of irradiated infrared rays.
Fig. 15 is a diagram showing a spectrum diagram of an infrared spectrum of an Ra4 crystal. The vertical axis represents the transmittance, and the horizontal axis represents the wave number of irradiated infrared rays.
Fig. 16 is a diagram showing a spectrum diagram of a Raman spectrum of an Ra1-type crystal. The vertical axis represents the intensity, and the horizontal axis represents the number of Raman shifts.
Fig. 17 is a diagram showing a spectrum diagram of a Raman spectrum of a Ra2 crystal. The vertical axis represents the intensity, and the horizontal axis represents the number of Raman shifts.
Fig. 18 is a diagram showing a spectrum diagram of a Raman spectrum of an Ra3-type crystal. The vertical axis represents the intensity, and the horizontal axis represents the number of Raman shifts.
19 is a diagram showing a spectrum diagram of a Raman spectrum of a Ra4 crystal. The vertical axis represents the intensity, and the horizontal axis represents the number of Raman shifts.
Fig. 20 is a diagram showing an optical microscope photograph of an Ra1-type crystal.
Fig. 21 is a diagram showing an optical microscope photograph of an Ra2-type crystal.
Fig. 22 is a diagram showing an optical microscope photograph of an Ra3-type crystal.
Fig. 23 is a diagram showing an optical microscope photograph of an Ra4 crystal.

The present invention relates to novel crystals of Compound A (Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals). 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide is a compound having two kinds of enantiomers, R-form and S-form, and Compound A is an equivalent mixture thereof, that is, a racemate. In addition, the crystals of the present invention are those in which the R and S bodies are arranged with regularity in the crystal lattice in equal amounts, and they become Ra1 crystals, Ra2 crystals, or Ra3 crystals, respectively, depending on the production conditions.

The Ra4 crystal has a melting point of about 131 to 134°C, and in a powder X-ray diffraction pattern using Cu-Kα ray, diffraction peaks of 2θ values (°) are 5.8±0.2, 7.2±0.2, 8.6±0.2 , 13.8 ± 0.2, 16.3 ± 0.2, 16.7 ± 0.2, 17.4 ± 0.2, 17.7 ± 0.2, 19.4 ± 0.2, 19.8 ± 0.2, and 20.7 ± 0.2.

The Ra1 type crystal, the Ra2 type crystal, and the Ra3 type crystal each have the following physical properties.

The Ra1 crystal has a melting point of about 134 to 136° C., and in a powder X-ray diffraction pattern using Cu-Kα ray, as a diffraction peak of 2θ value (°),

7.1 ± 0.2, 8.6 ± 0.2, 8.9 ± 0.2, 9.1 ± 0.2, 13.3 ± 0.2, 14.0 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.0 ± 0.2, 16.4 ± 0.2, 20.3 ± 0.2, and 20.6 ± 0.2 It's a decision.

The Ra1-type crystal can be manufactured according to the following manufacturing method.

A required amount (for example, about 200 mg) of the Ra2 form crystal is heated in a suitable container (for example, a 20 mL sample bottle) at about 130° C. for a certain period of time (about 2 hours) to obtain the Ra1 form crystal.

The Ra2 crystal has a melting point of about 124 to 126°C, and in a powder X-ray diffraction pattern using Cu-Kα ray, as a diffraction peak of 2θ value (°),

4.3 ± 0.2, 8.5 ± 0.2, 10.8 ± 0.2, 11.4 ± 0.2, 12.4 ± 0.2, 12.8 ± 0.2, 15.1 ± 0.2, 16.1 ± 0.2, 16.8 ± 0.2, and 19.1 ± 0.2.

The Ra2-type crystal can be manufactured according to the following manufacturing method.

A required amount (eg, about 30 mg) of Compound A is dissolved in an appropriate amount (about 80 μL) of an organic solvent (eg, methanol) at about 60° C., and a certain amount of dissolution concentration (about 375 mg/mL) Prepare to become After the solution is cooled to room temperature, a laser is irradiated under constant conditions, and the solution is left still at about 20 DEG C to obtain Ra2 crystals.

Although laser irradiation conditions are as follows, it is not limited to this.

<Femtosecond laser>

Wavelength: 800 nm

Pulse width: 181 fs

Number of pulses: 125 pulses/10 seconds

As the organic solvent, an alcohol solvent is mentioned, for example, Preferably, a C1-C3 alkyl solvent is mentioned. Specifically, it is methanol, ethanol, a propanol, and isopropanol, and methanol is preferable.

Examples of the amount of the organic solvent include an amount in which a dissolution concentration of about 200 mg/mL to about 1000 mg/mL is achieved with respect to the organic solvent used in dissolving the compound A, and the dissolution concentration is preferably about 300 mg/L to about 500 mg/mL, for example, about 375 mg/mL.

The Ra3 crystal has a melting point of about 129 to 131°C, and in a powder X-ray diffraction pattern using Cu-Kα ray, as a diffraction peak of 2θ value (°),

3.6 ± 0.2, 7.1 ± 0.2, 7.4 ± 0.2, 9.6 ± 0.2, 11.9 ± 0.2, 12.5 ± 0.2, 12.9 ± 0.2, 14.3 ± 0.2, 15.7 ± 0.2, and 17.9 ± 0.2.

The Ra3-type crystal can be manufactured according to the following manufacturing method.

To a required amount (eg, about 100 mg) of the Ra1 form crystal prepared above, an appropriate amount (eg, about 1 mL) of an organic solvent is added, the suspension is heated to about 60°C, and constant conditions After stirring at low temperature (about 1000 rpm) for a certain period of time (about 2 days), the solvent is removed to obtain Ra3 crystals.

Examples of the organic solvent include an ether-based solvent, and preferably a dialkyl ether-based solvent composed of alkyl having 1 to 3 carbon atoms. Specific examples thereof include dimethyl ether, diethyl ether, dipropyl ether, and diisopropyl ether, and diisopropyl ether is preferable.

The amount of the organic solvent is in the range of 5 to 10 parts by weight, preferably 6 to 8 parts by weight, based on 1 part by weight of the Ra1-type crystal to be used.

At least one crystal selected from the group consisting of Ra1 crystals, Ra2 crystals, and Ra3 crystals is selected from the group consisting of the following groups (a), (b), (c), and (d) One or more components (hereinafter, referred to as the present component) may be mixed or used in combination.

The above mixture or combination means that at least one crystal selected from the group consisting of a Ra1 crystal, an Ra2 crystal, and an Ra3 crystal and the present component are used simultaneously, separately or at a time interval.

When the present component is used simultaneously with one or more crystals selected from the group consisting of Ra1 crystals, Ra2 crystals, and Ra3 crystals, at least one selected from the group consisting of Ra1 crystals, Ra2 crystals, and Ra3 crystals Crystals and this component may be contained in separate formulations, respectively, and may be contained in one formulation.

One aspect of the present invention provides at least one component selected from the group consisting of group (a), group (b), group (c), and group (d), and a crystal of the Ra1 form, the Ra2 form, and the Ra3 form. A composition containing one or more crystals selected from the group consisting of crystals (hereinafter, referred to as the composition of the present invention).

Group (a) includes acetylcholinesterase inhibitors (eg carbamate insecticides, organophosphorus insecticides), GABA agonist chlorine ion channel antagonists (eg phenylpyrazole insecticides), sodium channel modulators (eg pyrethane) Toroidal insecticides), nicotinic acetylcholine receptor antagonistic modulators (eg neonicotinoid insecticides), nicotinic acetylcholine receptor allosteric modulators, glutamic acid agonistic chlorine ion channel allosteric modulators (eg, macrolide insecticides), glazing hormone mimic, multisite inhibitor, synovial organ TRPV channel modulator, tick growth inhibitor, mitochondrial ATP biosynthesis enzyme inhibitor, oxidative phosphorylation deconjugation agent, nicotinic acetylcholine receptor channel blocker (e.g. For example, neristoxin-based insecticide), chitin synthesis inhibitor, moulting inhibitor, ecdysone receptor agonist, octopamine receptor agonist, inhibitor of mitochondrial electron transport system complex I, II, III and IV, potential-dependent sodium channel blocker, acetyl CoA carboxylase inhibitors, ryanodine receptor modulators (eg, diamide insecticides), choroidal organ modulators, active ingredients of microbial insecticides, and other insecticidal, acarid, and nematicidal active ingredients are the group consisting of . These are described in the classification based on the mechanism of action of the IRAC.

Group (b) includes nucleic acid synthesis inhibitors (eg, phenylamide-based fungicides, acylamino acid-based fungicides), cell division and cytoskeletal inhibitors (eg MBC fungicides), respiratory inhibitors (eg Qol fungicides, QiI fungicides), amino acid synthesis and protein synthesis inhibitors (eg, anilinopyridine-based fungicides), signal transduction inhibitors, lipid synthesis and membrane synthesis inhibitors, sterol biosynthesis inhibitors (eg, DMI fungicides such as triazole-based fungicides), cell wall Synthesis inhibitors, melanin synthesis inhibitors, plant defense inducers, point-of-action contact active fungicides, microorganism fungicides, and other bactericidal active ingredients. These are described in the classification based on the mechanism of action of the FRAC.

Group (c) is a group of plant growth regulating components (including mycorrhizal fungi and mycorrhizal fungi).

Group (d) is a group of repelling components consisting of a bird repelling component and an insect repelling component.

Hereinafter, examples of combinations of the present component with one or more crystals selected from the group consisting of Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals will be described. For example, alanikab (alanycarb) + SX means a combination of alanikab (alanycarb) and SX.

In addition, the abbreviation of SX means an Ra1-type crystal, Ra2-type crystal, or Ra3-type crystal|crystallization (henceforth, it describes as a crystal|crystallization of this invention). In addition, all of the present components described below are known components, and can be obtained from a commercially available formulation or can be manufactured by a known method. When this component is a microorganism, it can also be obtained from a fungal depository institution. Also, the number in parentheses indicates CAS RN (registered trademark).

Combination of this component of said group (a) with the inventive crystal:

abamectin + SX, acephate + SX, acequinocyl + SX, acetamiprid + SX, acetoprole + SX, acrinathrin + SX , acynonapyr + SX, afidopyropen + SX, afoxolaner + SX, alanycarb + SX, aldicarb + SX, allethrin ) + SX, alpha-cypermethrin + SX, alpha-endosulfan + SX, aluminum phosphide + SX, amitraz + SX, azadirachtin + SX, azamethiphos + SX, azinphos-ethyl + SX, azinphos-methyl + SX, azocyclotin + SX, Celastrus angulatus bark (bark of Celastrus) angulatus) + SX, bendiocarb + SX, benfluthrin + SX, benfuracarb + SX, bensultap + SX, benzoximate + SX, benz pyrimoxan + SX, beta-cyfluthrin + SX, beta-cypermethrin + SX, bifenazate + SX, bifenthrin + SX, bioallethrin + SX, bioresmethrin + SX, bistrifluron + SX, borax (bora) x) + SX, boric acid + SX, broflanilide + SX, bromopropylate + SX, buprofezin + SX, butocarboxim + SX , butoxycarboxim + SX, cadusafos + SX, calcium phosphide + SX, carbaryl + SX, carbofuran + SX, carbosulfan + SX, cartap hydrochloride + SX, cartap + SX, chinomethionat + SX, chlorantraniliprole + SX, chlordane + SX, chlore chlorethoxyfos + SX, chlorfenapyr + SX, chlorfenvinphos + SX, chlorfluazuron + SX, chlormephos + SX, chloropicrin + SX, chlorpyrifos + SX, chlorpyrifos-methyl + SX, chromafenozide + SX, clofentezine + SX, clothianidin + SX, concanamycin A + SX, coumaphos + SX, cryolite + SX, cyanophos + SX, cyantraniliprole + SX, cycla niliprole + SX, cycloprothrin + SX, cycloxaprid (cycloxa) prid) + SX, cyenopyrafen + SX, cyflumetofen + SX, cyfluthrin + SX, cyhalodiamide + SX, cyhalothrin ( cyhalothrin + SX, cyhexatin + SX, cypermethrin + SX, cyphenothrin + SX, cyromazine + SX, dazomet + SX, deltamet deltamethrin + SX, demeton-S-methyl + SX, diafenthiuron + SX, diazinon + SX, dichlorvos + SX, dichloro Mesotiaz (dicloromezotiaz) + SX, dicofol (dicofol) + SX, dicrotophos (dicrotophos) + SX, diflovidazin (diflovidazin) + SX, diflubenzuron (diflubenzuron) + SX, dimefluthrin (dimefluthrin) + SX, dimethoate + SX, dimethylvinphos + SX, dimpropyridaz + SX, dinotefuran + SX, disodium octaborate + SX , disulfoton + SX, DNOC (2-methyl-4,6-dinitrophenol) + SX, doramectin + SX, dried leaves of Dryopteris filix-mas + SX, emamectin benzoate (emamectin-benzoate) + SX, empenthrin + SX, endosulfan + SX, EPN (O-ethyl O-(4-nitrophenyl)phenylphos phonothioate + SX, epsilon-metofluthrin + SX, epsilon-momfluorothrin + SX, esfenvalerate + SX, ethiofencarb + SX, ethion + SX, ethiprole + SX, ethoprophos + SX, etofenprox + SX, etoxazole + SX, extract of Artemisia absinthium + SX, extract of Cassia nigricans (extract of Cassia nigricans) + SX, extract of clitoria ternatea + SX, extract of comfrey (extract of Symphytum officinale) + SX, extract of epazote (extracts or simulated) blend of Chenopodium ambrosioides) + SX, extract of Tanacetum vulgare + SX, extract of Urtica dioica + SX, mistletoe extract (extract of Viscum album) + SX, famphur + SX, fenamiphos + SX, fenazaquin + SX, fenbutatin oxide + SX, fenitrothion + SX, fenobucarb + SX, phenoxycarb ( fenoxycarb + SX, fenpropathrin + SX, fenpyroximate + SX, fenthion + SX, fenvalerate + SX, fipronil + SX, Plomethoquine (flometoquin) + SX, flonicamid + SX, fluacrypyrim + SX, fluazaindolizine + SX, fluazuron + SX, flubendiamide + SX, flucycloxuron + SX, flucythrinate + SX, fluensulfone + SX, flufenoprox + SX, flufenoxuron + SX , flufiprole + SX, flumethrin + SX, flupyradifurone + SX, flupyrimin + SX, fluralaner + SX, fluvalinate (fluvalinate) + SX, fluxametamide + SX, formetanate + SX, fosthiazate + SX, furamethrin + SX, furathiocarb + SX, gamma-cyhalothrin + SX, GS-omega/kappa HXTX-Hv1a peptide (GS-omega/kappa HXTX-Hv1a peptide) + SX, halfenprox + SX, halofenoza halofenozide + SX, heptafluthrin + SX, heptenophos + SX, hexaflumuron + SX, hexythiazox + SX, potassium salt of hopbetaic acid (potassium salt of hop beta acid) + SX, hydramethylnon + SX, hydroprene + SX, imicyafos + SX, imidacloprid + SX, imidaclothiz + SX, imiprothrin + SX, indoxacarb + SX, isocycloseram + SX, isopenphos ( isofenphos) + SX, isoprocarb + SX, isopropyl-O-(methoxyaminothiophosphoryl)salicylate) + SX, isoxathion + SX , ivermectin + SX, kadethrin + SX, kappa-tefluthrin + SX, kappa-bifenthrin + SX, kinoprene + SX, lambda cyhalothrin + SX, lenoremycin + SX, lepimectin + SX, lime sulfur + SX, lotilaner + SX, lufenuron ( lufenuron + SX, machine oil + SX, malathion + SX, mecarbam + SX, meperfluthrin + SX, metaflumizone + SX, metam (metam) + SX, metamidophos + SX, methidathion + SX, methiocarb + SX, methomyl + SX, methoprene + SX, me methoxychlor + SX, methoxyfenozide + SX, methyl bromide + SX, metofluthrin + SX, metolcarb ( metolcarb) + SX, metoxadiazone + SX, mevinphos + SX, milbemectin + SX, milbemycin oxime + SX, momfluorothrin + SX , monocrotophos + SX, moxidectin + SX, naled + SX, neem oil + SX, nicotine + SX, nicotine-sulfate + SX , nitenpyram + SX, novaluron + SX, noviflumuron + SX, oil of the seeds of Chenopodium anthelminticum + SX, omethoate + SX, oxamyl + SX, oxazosulfyl + SX, oxydemeton-methyl + SX, parathion + SX, parathion-methyl + SX, permethrin (permethrin) + SX, phenothrin + SX, pentoate + SX, phorate + SX, phosalone + SX, phosmet + SX, phosphamidone (phosphamidon) + SX, phosphine + SX, phoxim + SX, pirimicarb + SX, pyrimiphos-methyl + SX, prallethrin + SX , propenofos + SX, profluthrin + SX, propargite + SX, propetamphos + SX, propoxur + SX, propylene glycol alginate + SX, prothiofos + SX, pyflubumide + SX, pymetrozine + SX, pyraclofos ( pyraclofos + SX, pyrethrins + SX, pyridaben + SX, pyridalyl + SX, pyridaphenthion + SX, pyrifluquinazone + SX, pyri midifen + SX, pyriminostrobin + SX, pyriprole + SX, pyriproxyfen + SX, quinalphos + SX, resmethrin + SX, rotenone + SX, ryanodine + SX, sarolaner + SX, selamectin + SX, sigma-cypermethrin + SX, silafluorfen (silafluofen) + SX, sodium borate + SX, sodium metaborate + SX, spinetoram + SX, spinosad + SX, spirodiclofen + SX, spiromesifen + SX, spiropidion + SX, spirotetramat + SX, sulfluramid + SX, sulfotep + SX, sulfoxaflor (sulfoxaflor) + SX, sulfur + SX, sulfuryl fluoride + SX, tartar emetic + SX, tauflu tau-fluvalinate + SX, tebufenozide + SX, tebufenpyrad + SX, tebupirimfos + SX, teflubenzuron + SX, te tefluthrin + SX, temephos + SX, terbufos + SX, terpene constituents of the extract of chenopodium ambrosioides near ambrosioides + SX, tetrachlorantranil tetrachlorantraniliprole + SX, tetrachlorvinphos + SX, tetradifon + SX, tetramethrin + SX, tetramethylfluthrin + SX, tetraniliprole ( tetraniliprole) + SX, theta-cypermethrin + SX, thiacloprid + SX, thiamethoxam + SX, thiocyclam + SX, thiodicarb + SX, thiofanox + SX, thiometon + SX, thiosultap-disodium + SX, thiosultap-monosodium + SX, thioxazafen ) + SX, tolfenpyrad + SX, tralomethrin + SX, transfluthrin + SX, triazamate + SX, triazophos + SX, tri trichlorfon + SX, triflume zopyrim + SX, triflumuron + SX, trimethacarb + SX, tyclopyrazoflor + SX, vamidothion + SX, quasia amara wood extract ( wood extract of Quassia amara) + SX, XMC (3,5-dimethylphenyl N-methylcarbamate) + SX, xylylcarb (xylylcarb) + SX, zeta-cypermethrin + SX, zinc phosphide + SX, 4- [5- (3,5-dichlorophenyl) -5- (trifluoromethyl) -4,5-dihydro-1,2-oxazol-3-yl] -2-methyl-N- (1-oxothietan-3 -yl)benzamide (1241050-20-3) + SX, 3-methoxy-N-(5-{5-(trifluoromethyl)-5-[3-(trifluoromethyl)phenyl]-4,5-dihydro-1,2 -oxazol-3-yl}indan-1-yl)propanamide (1118626-57-5) + SX, 2-chloro-4-fluoro-5-{[5-(trifluoromethylthio)pentyl]oxy}phenyl 2,2, 2-trifluoroethyl sulfoxide (1472050-04-6) + SX, 4-chloro-5-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-methylphenyl 2,2,2- trifluoroethyl sulfoxide (1632218-00-8) + SX, 4-fluoro-5-[2,2-difluoro-2-(3,4,5-trifluorophenyl)ethoxy]-2-methylphenyl 2,2,2-trifluoroethyl sulfoxide (1632217-98-1) + SX, 2-({2-fluoro-4-methyl-5-[(2,2,2-trifluor) oethyl)sulfinyl]phenyl}imino)-3-(2,2,2-trifluoroethyl)-1,3-thiazolidin-4-one (1445683-71-5) + SX, (1Z)-2-(4-tert -butylphenyl)-2-cyano-1-(1-ethyl-3-methyl-1H-pyrazol-5-yl)ethenyl 2,2-dimethylpropanoate (1253429-01-4) + SX, N-[(1S,2S )-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)pyridine-3-carboxamide (1644251-74-0) + SX, (3R)-3-(2-chlorothiazol-5-yl)- 8-methyl-7-oxo-6-phenyl-2,3-dihydrothiazolo[3,2-a]pyrimidin-4-ium-5-olate (2249718-27-0) + SX, BT Crop protein Cry1Ab (BT crop protein Cry1Ab) + SX, BT crop protein Cry1Ac (BT crop protein Cry1Ac) + SX, BT crop protein Cry1Fa (BT crop protein Cry1Fa) + SX, BT crop protein Cry1A.105 (BT crop protein Cry1A.105) + SX, BT crop protein Cry2Ab (BT crop protein Cry2Ab) + SX, BT crop protein Vip3A (BT crop protein Vip3A) + SX, BT crop protein Cry3A (BT crop protein Cry3A) + SX, BT crop protein Cry3Ab (BT crop protein Cry3Ab) + SX, BT crop protein Cry3Bb (BT crop protein Cry3Bb) + SX, BT crop protein Cry34Ab1/Cry35Ab1 (BT crop protein Cry34Ab1/Cry35Ab1) + SX, Adoxofies aurana granule disease virus BV -0001 week ( Adoxophyes orana granulosis virus strain BV-0001) + SX, Anticarsia gemmatalis mNPV + SX, Autographa californica mNPV + SX, Cydia pomonella granulosis Virus strain V15 (Cydia pomonella GV strain V15) + SX, Cydia pomonella granulosis virus strain V22 (Cydia pomonella GV strain V22) + SX, Cryptophlebia leucotreta GV + SX, dend Dendrolimus punctatus cypovirus + SX, Helicoverpa armigera NPV strain BV-0003 + SX, Helicoverpa armigera NPV strain BV-0003 Helicoverpa zea NPV) + SX, Lymantria dispar NPV + SX, Mamestra brassicae NPV + SX, Mamestra configurata nuclear polyhedron virus ( Mamestra configurata NPV) + SX, Neodiprion abietis NPV + SX, Neodiprion lecontei NPV + SX, Neodiprion sertiper nuclear polyhedrosis Virus (Neodiprion sertifer NPV) + SX, Nosema locustae + SX, Orgyia pseudotsugata NPV + SX, Pieris rapae GV) + SX, Plodia interpunctella GV + SX, Spodoptera exigua mNPV + SX, Spodoptera littoralis mNPV) + SX, Spodoptera litura NPV + SX, Arthrobotrys dactyloides + SX, Bacillus firmus strain GB-126 + SX, Bacillus firmus strain I-1582 + SX, Bacillus megaterium + SX , Bacillus sp. strain AQ175 + SX, Bacillus sp. strain AQ177 + SX, Bacillus sp. strain AQ178 + SX, Bacillus sphaericus strain 2362 + SX, Bacillus sphaericus strain ABTS1743 + SX, Bacillus sphaericus Serotype strain H5a5b + SX, Bacillus thuringiensis strain AQ52 + SX, Bacillus thuringiensis strain BD#32 + SX, Bacillus thuringiensis strain CR-371 SX, Bacillus thuringiensis subsp. Aizawai strain ABTS-1857 + SX, Bacillus thuringiensis subsp. Aizawai strain AM65-52 + SX, Bacillus thuringiensis subsp. Aizawai strain GC-91 + SX, Bacillus thuringiensis subsp. Aizawai Serotype strain H-7 + SX, Bacillus thuringiensis subsp. Kurstaki strain ABTS351 + SX, Bacillus thuringiensis subsp. Kurstaki strain BMP123 + SX, Bacillus thuringiensis subsp. Kurstaki strain EG234 + SX, Bacillus thuringiensis subsp. Kurstaki strain EG7841 + SX, Bacillus thuringiensis subsp. Kurstaki strain EVB113-19 + SX, Bacillus thuringiensis subsp. Kurstaki strain F810 + SX, Bacillus thuringiensis subsp. Kurstaki strain HD-1 + SX, Bacillus thuringiensis subsp. Kurstaki strain PB54 + SX, Bacillus thuringiensis subsp. Kurstaki strain SA-11 + SX, Bacillus thuringiensis subsp. Kurstaki strain SA-12 + SX, Bacillus thuringiensis subsp. Tenebriosis strain NB176 + SX, Bacillus thuringiensis subsp. Thuringiensis strain MPPL002 + SX, Bacillus thuringiensis subsp. morrisoni + SX, Bacillus thuringiensis var. colmeri + SX, Bacillus thuringiensis var. darmstadiensis strain 24-91 + SX, Bacillus thuringiensis var. dendrolimus + SX, Bacillus thuringiensis var. galleriae + SX, Bacillus thuringiensis var. israelensis strain BMP144 + SX, Bacillus thuringiensis var. israelensis serotype strain H-14 + SX, Bacillus thuringiensis var. japonensis strain buibui + SX, Bacillus thuringiensis var. san diego strain M-7 + SX, Bacillus thuringiensis var. 7216 + SX, Bacillus thuringiensis var. aegypti + SX, Bacillus thuringiensis var. T36 + SX, Beauveria bassiana strain ANT-03 + SX, Beauveria bassiana strain ATCC74040 + SX, Beauveria bassiana strain GHA + SX, Beauveria brongniartii + SX, Burkholderia rinojensis strain A396 + SX, Chromobacterium subtsugae strain PRAA4-1T + SX, Dectylaria thaumasia + SX, Hirsutella minnesotensis + SX, Hirsutella rhossiliensis + SX, Hirsutella thompsonii + SX, Lagenidium giganteum + SX, Lecanicillium lecanii strain OM 499 + SX1 + SX, Lecanicillium conidillium of lecanicillii conidia of strain DA 96 + SX, Lecanicillium muscarium strain Ve6 + SX, Metarhizium anisopliae strain F52 + SX, Metarhizium anisopliae var. acridum + SX, Metarhizium anisopliae var. anisopliae BIPESCO 5/F52 + SX, Metarhizium flavoviride + SX, Monacrosporium phymatopagum + SX, Paecilomyces fumosoroseus Apopka strain 97 + SX, Paecilomyces lilacinus strain 251 + SX, Paecilomyces tenuipes strain T1 + nish Pisaibacillus strain 251 + SX, Paecilomyces tenuipes strain T1 + SX SX, Pasteuria penetrans + SX, Pasteuria usgae + SX, Pasteuria thoynei + SX, Serratia entomophila + SX, Verticillium chlamydosporium + SX, Verticillium lecani strain NCIM1312 + SX, 2-chloro-N-cyclopropyl-5-{1-[2, 6-dichloro-4-(1,1,1,2,3,3,3-heptafluoropropan-2-yl)phenyl]-1H-pyrazol-4-yl}-N-methylpyridine-3-carboxamide (1771741-86 -6) + SX, N-{4-chloro-3-[(1-cyanocyclopropyl)carbamoyl]phenyl}-1-methyl-4-(methanesulfonyl)-3-(1,1,2,2,2-pentafluoroethyl )-1H-pyrazole-3-carboxamide (1400768-21-9) + SX, 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2 ]tetradec-11-en-10-one (907187-07-9) + SX, 3-(4'-fluoro-2,4-dimethyl[1,1'-biphenyl]-3-yl)-4-hydroxy -8-oxa-1-azaspiro[4.5]dec-3-en-2-one (1031 385-91-7) + SX, N-[3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl]-2-(methanesulfonyl)propanamide (2396747-83-2) + SX , 2-isopropyl-5-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]-1,3,4-thiadiazole (2058052-95-0) + SX, 1,4-dimethyl -2-[2-(3-pyridinyl)-2H-indazol-5-yl]-1,2,4-triazolidine-3,5-dione (2171099-09-3) + SX, ciproplanilide ( cyproflanilide) + SX.

Combination of this component of said group (b) with the inventive crystal:

acibenzolar-S-methyl + SX, aldimorph + SX, amethoctradin + SX, aminopyrifen + SX, amisulbrom + SX, anilazine + SX, azaconazole + SX, azoxystrobin + SX, basic copper sulfate + SX, benalaxyl + SX, benalaxyl M ( benalaxyl-M) + SX, benodanil + SX, benomyl + SX, benthiavalicarb + SX, benthiavalicarb-isopropyl + SX, benzobindiflupyr (benzovindiflupyr) + SX, binapacryl + SX, biphenyl + SX, bitertanol + SX, bixafen + SX, blasticidin-S + SX, Bordeaux mixture + SX, boscalid + SX, bromothalonil + SX, bromuconazole + SX, bupirimate + SX, captafol ) + SX, captan + SX, carbendazim + SX, carboxin + SX, carpropamid + SX, chinomethionat + SX, chitin + SX, chloroneb + SX, chlorothalonil + SX, chlozolinate + SX, colletochlorin B + SX, copper (II) acetate (copper(II) acetate) + SX, copper (II) hydroxide (copper(II) hydroxide) + SX, basic copper oxychloride + SX, copper (II) sulfate (copper( II) sulfate) + SX, coumoxystrobin + SX, cyazofamid + SX, cyflufenamid + SX, cymoxanil + SX, cyproconazole ( cyproconazole + SX, cyprodinil + SX, diclobentiazox + SX, diclofluanid + SX, diclocymet + SX, diclomezine ( diclomezine + SX, dichloran + SX, diethofencarb + SX, difenoconazole + SX, diflumetorim + SX, dimethachlone + SX , dimethirimol + SX, dimethomorph + SX, dimoxystrobin + SX, diniconazole + SX, diniconazole M (diniconazole-M) + SX, dinocap + SX, dipotassium hydrogenphosphite + SX, dipymetitrone + SX, dithianon + SX, dodecylbenzenesulfonic acid bisethylenediamine copper (II) complex salt (dodecylbenzenesulphonic) acid bisethylenediamine copper(II) salt) + SX, dodemorph + SX, dodine + SX, edifenpho s) + SX, enoxastrobin + SX, epoxiconazole + SX, etaconazole + SX, etaboxam + SX, ethirimol + SX, et etridiazole + SX, extract from tea tree extract (extract from Melaleuca alternifolia) + SX, extract from Reynoutria sachalinensis + SX, extract from the cotyledons of lupine plantlets ("BLAD ")) + SX, garlic extract (extract of Allium sativum) + SX, horsetail extract (extract of Equisetum arvense) + SX, fennel extract (extract of Tropaeolum majus) + SX, famoxadone + SX, fenamidone + SX, fenaminstrobin + SX, fenarimol + SX, fenbuconazole + SX, fenfuram + SX, fenhexamide ( fenhexamid + SX, fenoxanil + SX, fenpiclonil + SX, fenpicoxamid + SX, fenpropidin + SX, fenpropimorph + SX, fenpyrazamine + SX, triphenyltin acetate + SX, fentin chloride + SX, triphenyltin hydroxide + SX, ferbam + SX, ferimzone + SX, florylpicoxamid + SX, fluazinam + SX, fludioxonil + SX, flufenoxystrobin + SX, fluindapyr + SX, flumorph + SX, flu fluopicolide + SX, fluopyram + SX, fluopimomide + SX, fluoroimide + SX, fluoxapiprolin + SX, fluoxastrobin ) + SX, fluquinconazole + SX, flusilazole + SX, flusulfamide + SX, flutianil + SX, flutolanil + SX, flutriafol + SX, fluxapyroxad + SX, folpet + SX, fosetyl + SX, fosetyl-aluminium + SX, fuberidazole ) + SX, furalaxyl + SX, furametpyr + SX, guazatine + SX, hexaconazole + SX, hymexazole + SX, imazalyl (imazalil) + SX, imibenconazole + SX, iminoctadine + SX, iminoctadine triacetate + SX, inpyrfluxam + SX, iodocarb + SX, ifconazole (ipconazole) + SX, iffentrifluconazole (ipfentrifluconazole) + SX, ifflufenoquin (ipflufenoquin) + SX, ifrobenfos (iprobenfos) + SX, iprodione + SX, iprovalicarb + SX, isopetamide + SX, isoflucypram + SX, isoprothiolane + SX, isopyrazam + SX, isotianil + SX, kasugamycin + SX, cresoxim-methyl + SX, laminarin + SX, of oak leaves and bark of Quercus + SX, mancozeb + SX, mandestrobin + SX, mandipropamid + SX, maneb + SX, mefen trifluconazole + SX, mepanipyrim + SX, mepronil + SX, meptyldinocap + SX, metalaxyl + SX, metalaxyl M (metalaxyl-M) ) + SX, metconazole + SX, metasulfocarb + SX, metiram + SX, metominostrobin + SX, metrafenone + SX, methyltetraprole + SX, mineral oils + SX, myclobutanil + SX, naftifine + SX, nuarimol + SX, octhilinone ) + SX, ofurace + SX, orysastrobin + SX, oxadixyl + SX, oxathiapiprolin + SX, oxine-c opper + SX, oxolinic acid + SX, oxpoconazole + SX, oxpoconazole fumarate + SX, oxycarboxin + SX, oxytetracycline + SX, pefurazoate + SX, penconazole + SX, pencycuron + SX, penflufen + SX, penthiopyrad + SX, phenamark phenamacril + SX, phosphorous acid + SX, phthalide + SX, picarbutrazox + SX, picoxystrobin + SX, piperalin + SX, polyoxins + SX, potassium hydrogencarbonate + SX, potassium dihydrogenphosphite + SX, probenazole + SX, prochloraz + SX, procymidone (procymidone) + SX, propamidine + SX, propamocarb + SX, propiconazole + SX, propineb + SX, proquinazid + SX, prothiocarb + SX, prothioconazole + SX, pydiflumetofen + SX, pyraclostrobin + SX, pyrametostrobin + SX , pyraoxystrobin + SX, pyrapropoyne + SX, pyraziflumid + SX, pyrazophos + SX, pyribencarb + SX, pyributicarb + SX, pyridachlometyl + SX, pyrifenox (pyrifenox) + SX, pyrimethanil + SX, pyrimorph + SX, pyriofenone + SX, pyrisoxazole + SX, pyroquilon + SX , Quillaja extract + SX, quinconazole + SX, quinofumelin + SX, quinoxyfen + SX, quintozene + SX, quinoa Saponins of Chenopodium quinoa + SX, sedaxane + SX, silthiofam + SX, simeconazole + SX, sodium hydrogencarbonate + SX, spiroxamine (spiroxamine) + SX, streptomycin + SX, sulfur + SX, tebuconazole + SX, tebufloquin + SX, teclofthalam + SX, technagen (tecnazene) + SX, terbinafine + SX, tetraconazole + SX, thiabendazole + SX, thifluzamide + SX, thiophanate + SX, thiophanate-methyl + SX, thiram + SX, thymol + SX, tiadinil + S X, tolclofos-methyl + SX, tolfenpyrad + SX, tolprocarb + SX, tolylfluanid + SX, triadimefon + SX , triadimenol + SX, triazoxide + SX, triclopyricarb + SX, tricyclazole + SX, tridemorph + SX, trifoxy trifloxystrobin + SX, triflumizole + SX, triforine + SX, triticonazole + SX, validamycin + SX, valifenalate + SX , vinclozolin + SX, yellow mustard powder + SX, zinc thiazole + SX, zineb + SX, ziram + SX, zoxamide + SX, N' -[4-({3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl}oxy)-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide (1202781-91 -6) + SX, N'-{4-[(4,5-dichlorothiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylmethanimidamide (929908-57-6) + SX , N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylmethanimidamide (1052688-31-9) + SX, N'-[5-choro-4-(2-fluorophenoxy)-2 -methylphenyl)-N-ethyl-N-methylmethani midamide (2055589-28-9) + SX, N'-[2-choro-4-(2-fluorophenoxy)-5-methylphenyl)-N-ethyl-N-methylmethanimidamide (2055756-21-1) + SX, N '-[4-(1-hydroxy-1-phenyl-2,2,2-trifluoroethyl)-2-methyl-5-methoxyphenyl)-N-isopropyl-N-methylmethanimidamide (2101814-55-3) + SX, N '-[5-bromo-6-(1-methyl-2-propoxyethoxy)-2-methylpyridin-3-yl)-N-ethyl-N-methylmethanimidamide (1817828-69-5) + SX, 4-(2- bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine (1362477-26-6) + SX, 2-[6-(3- fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline (1257056-97-5) + SX, 5-fluoro-4-imino-3-methyl-1-tosyl-3,4-dihydropyrimidin-2 ( 1H)-one (1616664-98-2) + SX, ethyl(2Z)-3-amino-2-cyano-3-phenylacrylate (39491-78-6) + SX, N-[(2-chlorothiazol-5- yl)methyl]-N-ethyl-6-methoxy-3-nitropyridin-2-amine (1446247-98-8) + SX, 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1- (1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1394057-11-4) + SX, (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl )-2-methyl-1-(1H-1,2,4-tri azol-1-ylmethyl)cyclopentan-1-ol (1801930-06-2) + SX, (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-( 1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-07-3) + SX, 2-(chloromethyl)-5-(4-fluorobenzyl)-2-methyl-1-( 1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1394057-13-6) + SX, (1R,2S,5S)-2-(chloromethyl)-5-(4-fluorobenzyl) -2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-08-4) + SX, (1S,2R,5R)-2-(chloromethyl) -5-(4-fluorobenzyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-ol (1801930-09-5) + SX, methyl 3-[( 4-chlorophenyl)methyl]-2-hydroxy-1-methyl-2-(1H-1,2,4-triazol-1-ylmethyl)cyclopentan-1-carboxylate (1791398-02-1) + SX, 1-( 2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)-1-[1-(4-bromo-2,6-difluorophenoxy)cyclopropyl]ethanol (2019215-86-0 ) + SX, 1-(2,4-difluorophenyl)-2-(1H-1,2,4-triazol-1-yl)-1-[1-(4-chloro-2,6-difluorophenoxy)cyclopropyl] ethanol (2019215-84-8) + SX, 1- [2- (1-chlorocyclopropyl) -3- (2-fluorophenyl) -2-hydroxypropyl] -1H-imidazole-5 -carbonitrile (2018316-13-5) + SX, 1- [2- (1-chlorocyclopropyl) -3- (2,3-difluorophenyl) -2-hydroxypropyl] -1H-imidazole-5-carbonitrile (2018317-25- 2) + SX, 4-({6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1H-1,2,4-triazol-1-yl)propyl ]pyridin-3-yl}oxy)benzonitrile (2046300-61-0) + SX, 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1-(1H-1, 2,4-triazol-1-yl)propan-2-ol (2082661-43-4) + SX, 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)pyridin-3-yl]-1- (1H-1,2,4-triazol-1-yl)propan-2-ol (2082660-27-1) + SX, methyl({2-methyl-5-[1-(4-methoxy-2-methylphenyl) )-1H-pyrazol-3-yl]phenyl}methyl)carbamate (1605879-98-8) + SX, 2-(difluoromethyl)-N-[1,1,3-trimethyl-2,3-dihydro-1H- inden-4-yl]pyridine-3-carboxamide (1616239-21-4) + SX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-2,3-dihydro-1H-inden- 4-yl]pyridine-3-carboxamide (1847460-02-9) + SX, 2-(difluoromethyl)-N-[3-propyl-1,1-dimethyl-2,3-dihydro-1H-inden-4- yl]pyridine-3-carboxamide (1847460-05-2) + SX, (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol -3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide (1445331-27-0) + SX, (2E,3Z)-5-{[1-(2,4- dichlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide (1445331-54-3) + SX, 5-chloro-4-({2-[ 6-(4-chlorophenoxy)pyridin-3-yl]ethyl}amino)-6-methylpyrimidine (1605340-92-8) + SX, N-(1-benzyl-1,3-dimethylbutyl)-8-fluoroquinoline-3 -carboxamide (2132414-04-9) + SX, N-(1-benzyl-3,3,3-trifluoro-1-methylpropyl)-8-fluoroquinoline-3-carboxamide (2132414-00-5) + SX, 4 ,4-dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one (2098918-25-1) + SX, 5 ,5-dimethyl-2-({4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}methyl)isoxazolidin-3-one (2098918-26-2) + SX, Agrobacterium radiobactor strain K1026 + SX, Agrobacterium radiobactor strain K84 + SX, Bacillus amyloliquefaciens (Aveo® EZ Nematicide) + SX, Bacillus amyloliquefaciens strain AT332 + SX, Bacillus amyloliquefaciens strain B3 + SX, Bacillus amyloliquefaciens strain B3 + SX, Bacillus amyloliquefaciens a myloliquefaciens strain DB101 + SX, Bacillus amyloliquefaciens strain DB102 + SX, Bacillus amyloliquefaciens strain GB03 + SX, Bacillus amyloliquefaciens strain FZB24 + SX, Bacillus amyloliquefaciens strain FZB42 + SX, Bacillus amyloliquefaciens strain FZB42 + SX, Bacillus amyloliquefaciens strain Bacillus amyloliquefaciens strain a strain QST713 + SX, Bacillus amyloliquefaciens isolate strain B246 + SX, Bacillus amyloliquefaciens strain F727 + SX, Bacillus amyloliquefaciens subsp. plantarum strain D747 + SX, Bacillus licheniformis strain HB-2 + SX, Bacillus licheniformis strain SB3086 + SX, Bacillus pumilus strain AQ717 + SX, Bacillus pumilus strain BUF-33 + SX, Bacillus pumilus strain GB34 + SX, Bacillus pumilus strain QST2808 + SX, Bacillus simplex strain CGF2856 + SX, Bacillus subtilis strain AQ153 + SX, Bacillus subtilis strain AQ743 + SX, Bacillus subtilis strain BU1814 + SX, Bacillus subtilis strain D747 + SX, Bacillus subtilis strain DB101 + SX, Bacillus subtilis strain FZB24 + SX , Bacillus subtilis strain GB03 + SX, Bacillus subtilis strain HAI0404 + SX, Bacillus subtilis strain IAB/BS03 + SX, Bacillus subtilis strain MBI600 + SX, Bacillus subtilis strain QST30002/AQ30002 + SX, Bacillus subtilis strain QST30004/AQ30004 subtilis strain QST713 + SX, Bacillus subtilis strain QST714 + SX, Bacillus subtilis var. Amyloliquefaciens strain FZB24 + SX, Bacillus subtilis strain Y1336 + SX, Burkholderia cepacia + SX, Burkholderia cepacia type Wisconsin strain J82 + SX, Burkholderia cepacia type Wisconsin strain M54 + SX, Candida oleophila strain O + saitoana strain M54 + SX, Candida oleophila strain O + saitoum + SX, Clonostachys rosea + SX, Coniothyrium minitans strain CGMCC8325 + SX, Coniothyrium minitans strain CON/M/91-8 + SX, cryptococcus albidus + SX, Erwinia carotovora subsp. carotovora strain CGE234M403 + SX, Fusarium oxysporum strain Fo47 + SX, Gliocladium catenulatum strain J1446 + SX, Paenibacillus polymyxa strain AC-1 + SX, Paenibacillus polymyxa strain BS-0105 + SX, Pantoea agglomerans strain E325 + SX, VRApsi strain E325 + s SX, Phlebio199 SX, Pseudomonas aureofaciens strain TX-1 + SX, Pseudomonas chlororaphis strain 63-28 + SX, Pseudomonas chlororaphis strain AFS009 + SX, Pseudomonas chlororaphis strain MA342 + SX, Pseudomonas fluorescens strain, Pseudomonas AFS009 + SX, Pseudomonas fluorescens strain MA342 + SX, Pseudomonas fluorescens strain, Pseudomonas SX, Pseudomonas fluorescens strain 1629RS strain CL145A + SX, Pseudomonas fluorescens strain G7090 + SX, Pseudomonas sp. strain CAB-02 + SX, Pseudomonas syringae strain 742RS + SX, Pseudomonas syringae strain MA-4 + SX, Pseudozyma flocculosa strain PF-A22UL + SX, Pseudomonas rhodesiae strain HAI-0804 + SX, Pythium oligandrum strain DV strain M1 + SX, Streptomyces griseoviridis strain K61 + SX, Streptomyces lydicus strain WYCD108US + SX, Streptomyces lydicus strain WYEC108 + SX, Talaromyces flavus strain SAY-Y-94-01 + SX, Talaromyces flavus strain V117b + SX, Trichoderma asperell strain ICC012 + SX, Trichoderma asperellum SKT-1 + SX, Trichoderma asperellum strain T25 + SX, Trichoderma asperellum strain T34 + SX, Trichoderma asperellum strain TV1 + SX, Trichoderma atroviride strain CNCM 1-1237 + SX, Trichoderma atroviride strain LC52 + SX atroviride strain IMI 206040 + SX, Trichoderma atroviride strain SC1 + SX, Trichoderma atroviride strain SKT-1 + SX, Trichoderma atroviride strain T11 + SX, Trichoderma gamsii strain ICC080 + SX, Trichoderma harzianum strain 21 + SX, Trichoderma harzianum strain DB104 + SX, Trichoderma harzianum strain DSM 14944 + SX, Trichoderma harzianum strain ESALQ-1303 + SX, Trichoderma harzianum strain ESALQ-1306 + SX, Trichoderma harzianum strain IIHR-Thderma harz, IHR-Thderma harz, SX, 908 + SX, Trichoderma harzianum strain kd + SX, Trichoderma harzianum strain MO1 + SX, Trichoderma harzianum strain SF + SX, Trichoderma harzianum strain T22 + SX, Trichoderma harzianum strain T39 + SX, Trichoderma harzianum strain TH35 + T78 SX, Trichoderma polysporum strain IMI206039 + SX, trichoderma stromaticum + SX, Trichoderma virens strain G-41 + SX, Trichoderma virens strain GL-21 + SX, Trichoderma viride + SX, Variovorax paradoxus strain CGF4526 + SX, Harpin protein + SX Benetheram (flubeneteram) + SX, N-acetyl-2-(ethanesulfonyl)-N-[2-(methoxycarbonyl)-4-(trifluoromethoxy)phenyl]-4-(trifluoromethyl)benzamide (2043675-28-9) + SX , (2S,3S)-3-(2-methylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypy ridin-2-yl)carbonyl]-L-alaninate (2376210-00-1) + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-[(3- acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-[(3-acetoxy-4 -methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-[(3-acetoxy-4-methoxypyridin-2- yl)carbonyl]-L-alaninate (2376209-13-9) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy] -4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376210-02-3) + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-( {3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2- yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376209-40-2) + SX, (2S,3S)-3-(2 ,4-dimethylphenyl)butan-2-yl N-({3-[(2-methylpropanoyl)oxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate (2376209-15-1) + SX, N '-(2-choro-4-phenoxy-5-methylphenyl)-N-ethyl-N-methylmethanimida mide (2062599-39-5) + SX, (2S,3S)-3-(2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L- alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX , (2S,3S)-3-(4-methoxy-2-methylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S ,3S)-3-(2,4-dimethylphenyl)butan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3 -(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3 -(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3 -(2,4-difluorophenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-( 2,4-dimethylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4- fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-[(3-acetoxy-4-met hoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy)- 4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy )-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy )-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl)-4-methylpentan-2-yl N-{[3-(acetoxymethoxy )-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-{[3- (acetoxymethoxy)-4-methoxypyridin-2-yl]carbonyl}-L-alaninate + SX, (2S,3S)-3-(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-({ 3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2-fluoro-4-methylphenyl)-4-methylpentan-2- yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2,4-difluorophenyl)-4-methylpenta n-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(2,4-dimethylphenyl) -4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3-(4-fluoro -2-methoxylphenyl)-4-methylpentan-2-yl N-({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)-L-alaninate + SX, (2S,3S)-3 -(4-fluoro-2-methylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3 -(2-fluoro-4-methylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3 -(2,4-difluorophenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-( 2,4-dimethylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX, (2S,3S)-3-(4- fluoro-2-methoxylphenyl)-4-methylpentan-2-yl N-[(3-hydroxy-4-methoxypyridin-2-yl)carbonyl]-L-alaninate + SX.

Combination of this component of said group (c) with the inventive crystal:

1-methylcyclopropene + SX, 1,3-diphenylurea (1,3-diphenylurea) + SX, 2,3,5-triiodobenzoic acid (2,3,5-triiodobenzoic acid) + SX, IAA ((1H-indol-3-yl)acetic acid) + SX, IBA (4-(1H-indol-3-yl)butyric acid) + SX, MCPA (2-(4-chloro-2- methylphenoxy)acetic acid) + SX, MCPB (4-(4-chloro-2-methylphenoxy)butyric acid) + SX, 4-CPA (4-chlorophenoxyacetic acid) + SX, 5-aminolevulinic acid hydrochloride (5-aminolevulinic acid) acid hydrochloride) + SX, 6-benzylaminopurine + SX, abscisic acid + SX, AVG (aminoethoxyvinylglycine) + SX, ancymidol + SX, butralin + SX, calcium carbonate + SX, calcium chloride + SX, calcium formate + SX, calcium peroxide + SX, lime sulfur (calcium polysulfide) + SX, calcium sulfate sulfate) + SX, chlormequat-chloride + SX, chlorpropham + SX, choline chloride + SX, cloprop + SX, cyanamide + SX, cyclanilide + SX, daminozide + SX, decan-1-ol + SX, dichlorprop + SX, dikegulac ( dikegulac + SX, dimethipin + SX, diquat + SX, ethephon + SX, ethychlozate + SX, flumetralin + SX, flu Flurprimidol + SX, forchlorfenuron + SX, formononetin + SX, Gibberellin A + SX, Gibberellin A3 + SX, inabenfide ) + SX, Kinetin + SX, lipochitooligosaccharide SP104 + SX, maleic hydrazide + SX, mefluidide + SX, mepiquat-chloride + SX, oxidation oxidized glutathione + SX, pacrobutrazol + SX, pendimethalin + SX, prohexadione-calcium + SX, prohydrojasmon + SX, pyra pyraflufen-ethyl + SX, sintofen + SX, sodium 1-naphthaleneacetate + SX, sodium cyanate + SX, streptmycin + SX, thidiazuron + SX, triapenthenol + SX, tribufos + SX, trinexapac-ethyl + SX, uniconazole P (uniconazole-P) + SX, 2-(naphthalen-1-yl)acetamide (2-(naphthalen-1-yl)acetamide) + SX, [4-oxo -4- (2-phenylethyl) amino] butyric acid + SX, 5- (trifluoromethyl) benzo [b] thiophene-2-methyl carboxylate + SX, 3-[(6-chloro-4-phenyl) Quinazolin-2-yl)amino]-1-propanol + SX, Claroideoglomus etunicatum + SX, Claroideoglomus claroideum + SX, Funneliformis mosseae + SX, Gigaspora margarita + SX, Gigaspora rosea + SX, Glomus aggregatum + SX, Glomus deserticola , Glomus monosporum + SX, Paraglomus brasillianum + SX, Rhizophagus clarus + SX, Rhizophagus intraradices RTI-801 + SX, Rhizophagus irregularis DAOM 197198 + SX, Azorhizobium caulinodans + SX, Azospirillum amazonense + SX, Azorhizobium caulinodans + SX, Azospirillum amazonense + SX -V5 + SX; Azospirillum brasilense Ab-V6 + SX; -11 + SX, Bradyrhizobium japonicum USDA 110 + SX, Bradyrhizobium liaoningense + SX, Bradyrhizobium lupini + SX, Delftia acidovorans RAY209 + SX, Mesor hizobium ciceri + SX, Mesorhizobium huakii + SX, Mesorhizobium loti + SX, Rhizobium etli + SX, Rhizobium galegae + SX, Rhizobium leguminosarum bv. Phaseoli + SX, Rhizobium leguminosarum bv. Trifolii + SX, Rhizobium leguminosarum bv. Viciae + SX, Rhizobium trifolii + SX, Rhizobium tropici + SX, Sinorhizobium fredii + SX, Sinorhizobium meliloti + SX, Zucchini Yellow Mosaik Virus weak strain + SX.

Combination of this component of said group (d) with the inventive crystal:

anthraquinone + SX, deet + SX, icaridin + SX.

The ratio of the crystals of the present invention to the present component is not particularly limited, but by weight ratio (crystals of the present invention: this component) 1000:1 to 1:1000, 500:1 to 1:500, 100:1 to 1:100, 50 : 1, 20 : 1, 10 : 1, 9: 1, 8 : 1, 7 : 1, 6 : 1, 5 : 1, 4 : 1, 3 : 1, 2 : 1, 1 : 1, 1 : 2, 1: 3, 1: 4, 1: 5, 1: 6, 1: 7, 1: 8, 1: 9, 1: 10, 1: 20, 1: 50, and the like.

Crystals of the present invention can be mixed or used in combination with chemical fertilizers (such as oil eye, phosphorus eye, draft eye, urea, and salt eye).

The crystals of the present invention or the composition of the present invention can control plant diseases caused by plant pathogenic microorganisms such as fungi, Oomycete, Phytomyxea, and bacteria. Examples of the fungus include Ascomycota, Basidiomycota, Blasocladiomycota, Chytridiomycota, Mucoromycota and Olpidiomycota. Plant diseases include the following. In parentheses, the scientific name of the plant pathogenic microorganism causing the disease is shown.

Rice diseases: blast disease (Pyricularia oryzae), cochlea blight (Cochliobolus miyabeanus), leaf blight (Rhizoctonia solani), marigold (Gibberella fujikuroi), yellow atrophy (Sclerophthora macrospora), scabie blast disease and toil disease (Epicoccum ni) Injury disease (Trichoderma viride, Rhizopus oryzae) ;

Wheat diseases: powdery mildew (Blumeria graminis), red mold disease (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), red rust (Puccinia recondita), Microdochium nivale, Microdochium majus, Typhula incarnata, Typhula ishikariensis) ;

Root diseases: powdery mildew (Blumeria graminis), red mold disease (Fusarium graminearum, Fusarium avenaceum, Fusarium culmorum, Microdochium nivale), yellow rust (Puccinia striiformis), black rust (Puccinia graminis), small rust (Puccinia hordei), Bacteria (Ustilago nuda), Rhynchosporium secalis, Pyrenophora teres, Spot (Cochliobolus sativus), Haemophilia (Pyrenophora graminea), Ramularia leaf spot disease (Ramularia collo-cygni), Rhizoctonia Leaf sheath blight caused by (Rhizoctonia solani) ;

Corn diseases: rust (Puccinia sorghi), southern rust (Puccinia polysora), leaf blight (Setosphaeria turcica), tropical rust (Physopella zeae), sesame (Cochliobolus heterostrophus), anthrax (Colletotrichum graminicola), gray leaf spot disease Cercospora zeae-maydis), gallbladder disease (Kabatiella zeae), Phaeosphaeria leaf spot disease (Phaeosphaeria maydis), Diplodia disease (Stenocarpella maydis, Stenocarpella macrospora), Stokes disease (Fusarium graminearum, Fusarium verticihumlioides, Colletotrichumlioides, Colletotrichum graminicola) Ustilago maydis), Brown spot disease (Physoderma maydis) ;

Cotton diseases: anthrax (Colletotrichum gossypii), white mold (Ramularia areola), black spot (Alternaria macrospora, Alternaria gossypii), black root rot disease (Thielaviopsis basicola) ;

Coffee diseases: rust (Hemileia vastatrix), leaf spot disease (Cercospora coffeicola);

Diseases of rapeseed: Sclerotinia sclerotiorum, Alternaria brassicae, Phoma lingam, light leaf spot disease (Pyrenopeziza brassicae) ;

Diseases of sugar cane: rust (Puccinia melanocephela, Puccinia kuehnii), black cane (Ustilago scitaminea);

Sunflower diseases: rust (Puccinia helianthi), downy mildew (Plasmopara halstedii);

Citrus diseases: sunspot (Diaporthe citri), window blight (Elsinoe fawcetti), green mold (Penicillium digitatum), blue mold (Penicillium italicum), late blight (Phytophthora parasitica, Phytophthora citrophthora), black mold (Aspergillus niger);

Apple diseases: Monilinia mali, Valsa ceratosperma, Powdery mildew (Podosphaera leucotricha), Spotted leaf blight (Alternaria alternata apple pathotype), Black star blight (Venturia inaequalis), Anthrax (Glomerella cingulata, Colletotrica), Diplocarpon mali, Botryosphaeria berengeriana, Phytophtora cactorum, Gymnosporangium juniperi-virginianae, Gymnosporangium yamadae;

Pear diseases: black star blight (Venturia nashicola, Venturia pirina), black spot blight (Alternaria alternata Japanese pear pathotype), red star blight (Gymnosporangium haraeanum) ;

Peach diseases: Monilinia fructicola, Cladosporium carpophilum, Phomopsis sp., Taphrina deformans;

Grape diseases: bird's eye disease (Elsinoe ampelina), bay leaf (Glomerella cingulata, Colletotrichum acutatum), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsidis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola);

Diseases of persimmon: anthrax (Gloeosporium kaki, Colletotrichum acutatum), deciduous disease (Cercospora kaki, Mycosphaerella nawae);

Diseases of figs: rust (Phakopsora nishidana) ;

Blight diseases: anthracnose (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), blight (Didymella bryoniae), brown blight (Corynespora cassiicola), creeper disease (Fusarium oxysporum), downy mildew (Pseudora capsicipora cube), downy mildew (Pseudoperonicipora) disease (Pythium sp.) ;

Diseases of tomatoes: Rotten blight (Alternaria solani), leaf mold (Cladosporium fulvum), black leaf mold (Pseudocercospora fuligena), late blight (Phytophthora infestans), powdery mildew (Leveillula taurica);

Eggplant diseases: Phomopsis vexans, powdery mildew (Erysiphe cichoracearum);

Diseases of cress: black spot (Alternaria japonica), vitiligo (Cercosporella brassicae), root lump (Plasmodiophora brassicae), downy mildew (Peronospora parasitica), white rust (Albugo candida);

Diseases of green onions: rust (Puccinia allii) ;

Soybean diseases: purpura (Cercospora kikuchii), black bean disease (Elsinoe glycines), sunspot disease (Diaporthe phaseolorum var. sojae), rust (Phakopsora pachyrhizi), brown rot (Corynespora cassiicola), anthrax (Colletotrichum glycines), colletotrichum glycines (Colletotrichum glycines) (Rhizoctonia solani), brown blight (Septoria glycines), spot blight (Cercospora sojina), sclerotinia sclerotiorum (Sclerotinia sclerotiorum), powdery mildew (Microsphaera diffusa), stem blight (Phytophthora sojae), downy mildew (Fronosguliformium), vironospora manshurica Black root rot (Calonectria iliicicola), Diaporthe/Phomopsis complex (Diaporthe longicolla) ;

Kidney bean diseases: Sclerotinia sclerotiorum, Uromyces appendiculatus, Phaeoisariopsis griseola, anthrax (Colletotrichum lindemuthianum), root rot (Fusarium solani);

Diseases of peanuts: Cercospora personata, Cercospora arachidicola, Sclerotium rolfsii, black root rot (Calonectria iliicicola);

Pea diseases: powdery mildew (Erysiphe pisi), root rot (Fusarium solani);

Potato diseases: summer blight (Alternaria solani), blight (Phytophthora infestans), color rot (Phytophthora erythroseptica), spongospora subterranea f. sp. subterranea (Verticillium albo-atrum, Verticillium dahliae) ), tendon disease (Fusarium solani), carcinoid disease (Synchytrium endobioticum) ;

Strawberry diseases: powdery mildew (Sphaerotheca humuli);

Diseases of tea: Exobasidium reticulatum, Elsinoe leucospila, rotational spot (Pestalotiopsis sp.), anthrax (Colletotrichum theae-sinensis) ;

Tobacco diseases: red star blight (Alternaria longipes), anthrax (Colletotrichum tabacum), downy mildew (Peronospora tabacina), late blight (Phytophthora nicotianae);

Sugar beet diseases: galvan (Cercospora beticola), leaf rot (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris), black root disease (Aphanomyces cochlioides), rust (Uromyces betae);

Diseases of roses: black star blight (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa);

Diseases of chrysanthemum: Galvan (Septoria chrysanthemi-indici), white rust (Puccinia horiana) ;

Onion diseases: vitiligo (Botrytis cinerea, Botrytis byssoidea, Botrytis squamosa), gray rot (Botrytis allii), microscopic sclerotia (Botrytis squamosa);

Various crop diseases: gray mold disease (Botrytis cinerea), sclerotinia sclerotiorum (Sclerotinia sclerotiorum), seedling disease (Pythium aphanidermatum, Pythium irregulare, Pythium ultimum);

Radish disease: black spot (Alternaria brassicicola) ;

Grass diseases: dollar spot disease (Sclerotinia homoeocarpa), brown patch disease, large patch disease (Rhizoctonia solani), red spot disease (Pythium aphanidermatum);

Banana disease: Shigatoka disease (Mycosphaerella fijiensis, Mycosphaerella musicola);

Diseases of lentils: Ascochyta disease (Ascochyta lentis) ;

Diseases of chickpeas: Ascochyta disease (Ascochyta rabei) ;

Diseases of bell peppers: anthrax (Colletotrichum scovillei) ;

Diseases of Mango: Anthrax (Colletotrichum acutatum) ;

Diseases of fruit trees: Rosellinia necatrix, Helicobasidium mompa;

Diseases of fruits such as apples and pears after harvest: Mucor piriformis;

Seed diseases or diseases in the early stages of growth caused by Aspergillus, Penicillium, Fusarium, Gibberella, Tricoderma, Thielaviopsis, Rhizopus, Mucor, Corticium, Phoma, Rhizoctonia, Diplodia, etc.;

Viral diseases: Big Bain's disease of lettuce mediated by Olpidium brassicae, viral diseases of various crops mediated by the genus Polymyxa (eg Polymyxa betae and Polymyxa graminis);

Diseases caused by bacteria: Burkholderia plantarii on rice, Pseudomonas syringae pv. Lachrymans on cucumbers, Ralstonia solanacearum on eggplants, Xanthomonas citri on citrus ulcers (Xanthomonas citri) (Erwinia carotovora), potato spear disease (Streptomyces scabiei), maize Goss' wilt disease (Clavibacter michiganensis), Pierce disease (Xylella fastidiosa) on grapes, olives, peaches, etc. Agrobacterium tumefaciens).

The method for controlling a plant disease of the present invention is carried out by treating a plant or soil with an effective amount of the present crystal or the composition of the present invention. As a treatment method, a foliage treatment, a soil treatment, and a seed treatment are mentioned, for example.

The crystals of the present invention or the composition of the present invention are usually mixed with an inert carrier such as a solid carrier and a liquid carrier, and, if necessary, a surfactant and other preparation auxiliaries are added to form a solid preparation, an aqueous suspension preparation, etc. do. These preparations contain the crystals of the present invention or the composition of the present invention in a weight ratio of usually 0.0001 to 99%.

Examples of the solid carrier include clays (kaolin clay, diatomaceous earth, bentonite, acid clay, etc.), fumed silica, wet silica, talc, ceramics, and other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate). Fine powders and granular materials such as, synthetic resins (polypropylene, polyacrylonitrile, polymethyl methacrylate, polyester resins such as polyethylene terephthalate, nylon resins such as nylon-6, nylon-11 and nylon-66) , polyamide resin, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-propylene copolymer, etc.) are mentioned.

As the liquid carrier, for example, water, alcohols (methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, phenoxyethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, dodecylbenzene, phenylxylylethane, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters ( Ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate, propylene glycol monomethyl ether acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ether (diisopropyl ether, 1,4-dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3- Methoxy-3-methyl-1-butanol, etc.), amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), sulfoxides (dimethyl sulfoxide, etc.), propylene carbonate and vegetable oils (soybean oil) , cottonseed oil, etc.).

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester, and anionic surfactants such as alkyl sulfonates, alkylbenzene sulfonates, and alkyl sulfates. can be heard Specifically, Nimbus (registered trademark), Assist (registered trademark), Aureo (registered trademark), Iharol (registered trademark), Silwet L-77 (registered trademark), BreakThru (registered trademark), SundanceII (registered trademark), Induce (registered trademark), Penetrator (registered trademark), AgriDex (registered trademark), Lutensol A8 (registered trademark), NP-7 (registered trademark), Triton (registered trademark), Nufilm (registered trademark), Emulgator NP7 (registered trademark) , Emulad (registered trademark), TRITON X 45 (registered trademark), AGRAL 90 (registered trademark), AGROTIN (registered trademark), ARPON (registered trademark), EnSpray N (registered trademark), and BANOLE (registered trademark), etc. can

Examples of other auxiliary agents for formulations include thickeners, antifoaming agents, preservatives, and cryoprotectants.

As a thickener, For example, natural polysaccharides, such as xanthan gum, ramic acid gum, locust bean gum, guar gum, carrageenan, welan gum, alginic acid, alginate, tragant gum; mineral powders such as aluminum silicate, magnesium aluminum silicate, smectite, bentonite, hectorite, synthetic hydrous silicic acid, and fumed silica; and alumina sol.

When this invention composition contains a thickener, the total content is 0.1 to 5 weight% normally with respect to 100 weight% of this invention composition.

As an antifoaming agent, For example, Antifoam C Emulsion (Toray Dow Corning Co., Ltd. brand name), Antifoam CE (Toray Dow Corning Co., Ltd. brand name), Antifoam A compound (Toray Dow Corning Co., Ltd. brand name), FS Antifoam 1266 ( Toray Dow Corning Co., Ltd. trade name), KM-98 (Shin-etsu Chemical Industry Co., Ltd. trade name), KS-530 (Shin-etsu Chemical Industry Co., Ltd. trade name), KS-538 (Shin-etsu Chemical Industry Co., Ltd. trade name), Breakthrough AF5503 (Evonik Industries AG) Company brand name), Antiform E-20 (Kao Corporation brand name), TSA730 (Momentive Performance Materials Japan joint company brand name), TSA731 (Momentive Performance Materials Japan joint company brand name), TSA732 (Momen) Silicone-based defoaming agents, such as TV Performance Materials Japan joint company brand name) and YMA6509 (Momentive Performance Materials Japan joint company brand name); and Fluorine-based antifoaming agents such as Fluwet PL80 (trade name of Clariant Corporation); Formstar W220 (Cognis Japan Co., Ltd. brand name) is mentioned.

When this invention composition contains an antifoamer, the total content is 0.05 to 0.5 weight% normally with respect to 100 weight% of this invention composition.

Preservatives include, for example, p-hydroxybenzoic acid ester, salicylic acid derivative, 1,2-benzoisothiazolin-3-one (eg, Proxel GXL (trade name of Lonza)) and isothiazoline-3- On derivatives (For example, Biohope L (K-I Chemicals trade name)) is mentioned.

When this invention composition contains a preservative, the total content is 0.01 to 3 weight% normally with respect to 100 weight% of this invention composition.

Examples of the cryoprotectant include water-soluble glycols such as ethylene glycol and propylene glycol.

When the composition of the present invention contains a cryoprotectant, the total content is usually 1 to 20% by weight based on 100% by weight of the composition of the present invention.

In the present invention, the plant includes the whole plant and a specific part of the plant. Particular parts of plants include, for example, foliage, flowers, ears, fruits, stems, branches, crowns, seeds, vegetative reproductive organs and seedlings.

The vegetative reproductive organ means, among the roots, stems, leaves, etc. of a plant, having the ability to grow when the parts are separated from the body and installed in the soil. As vegetative reproductive organs, for example, tuberous root, creeping root, bulb, corm or solid bulb, tuber, rhizome, stolon ), rhizophores, cane cuttings, propagules and vine cuttings. In addition, crawling is sometimes called a runner, and a young woman is also called a main child, and is divided into a broad bud and a bullbil. The vine means a seedling (a generic term for leaves and stems, shoots) such as sweet potatoes or yam. The rhizomes, stalks, tubers, rhizomes, stem fragments, dipped bodies, or tubers are collectively referred to as bulbs. The cultivation of tubers begins by planting the tubers in the soil, but the tubers used are commonly referred to as bell-beams.

The application amount of the crystal of the present invention or the composition of the present invention varies depending on weather conditions, formulation form, application time, application method, application site, target disease, target crop, etc., but in the case of foliage treatment or soil treatment, per 1000 m 2, It is usually 1-500 g. In the case of seed treatment, the quantity of this invention crystal|crystallization or this invention composition is 0.001-100g normally with respect to 1 Kg of seeds. When the crystals of the present invention or the composition of the present invention are formulated as an emulsion, wettable powder, flowable agent, etc., it is usually applied by diluting with water so that the concentration of the active ingredient is 0.01 to 10000 ppm, and powders, granules, etc. are usually applied as they are.

The seed treatment includes, for example, treatment of the present crystal or the present composition to seeds or vegetative reproductive organs, and specifically, for example, the present crystal or a suspension of the present invention in a mist form. A spray treatment for spraying the seed surface or the surface of a vegetative reproductive organ, a smear treatment for applying the crystals of the present invention or the composition of the present invention to the seeds or vegetative reproductive organs, immersing the seeds in the chemical solution of the crystals of the present invention or the composition of the present invention for a certain period of time Immersion treatment, a method of coating seeds or vegetative reproductive organs with a carrier containing the crystals of the present invention or the composition of the present invention (film coat treatment, pellet coat treatment, etc.) are mentioned. Examples of the vegetative reproductive organs include, in particular, cattle.

When the composition of the present invention is treated with seeds or vegetative reproductive organs, the present composition may be treated as a single preparation to the seeds or vegetative reproductive organs, or the present composition may be divided into a plurality of different preparations for seed or nutrient reproductive organs It can also be processed into the reproductive system. As a method of dividing the composition of the present invention into a plurality of different preparations and treating it in plural times, for example, a preparation containing only the crystals of the present invention as an active ingredient is treated, the seeds or vegetative reproductive organs are air-dried, and then this ingredient is a method of treating a formulation comprising; and a method of treating a formulation containing the crystals of the present invention and this component as active ingredients, air-drying the seeds or vegetative reproductive organs, and then treating a formulation containing the present component other than the treated product.

The seed or vegetative reproductive organ bearing the crystals of the present invention or the composition of the present invention in the present invention means a state in which the crystals of the present invention or the composition of the present invention are adhered to the surface of the seed or vegetative reproductive organ. In the seed or vegetative reproductive organ bearing the crystals of the present invention or the composition of the present invention, before and after the crystals of the present invention or the composition of the present invention are adhered to the seeds or vegetative reproductive organs, materials other than the crystals of the present invention or the composition of the present invention may be attached.

In addition, when the composition of the present invention is adhered as a layer to the surface of a seed or a vegetative reproductive organ, the layer consists of one layer or a plurality of layers. Moreover, when it consists of a plurality of layers, each layer is a layer containing one or more active ingredients, or consists of a layer containing one or more active ingredients and a layer not containing an active ingredient.

The seed or vegetative reproductive organ bearing the crystals of the present invention or the composition of the present invention can be prepared by, for example, applying a formulation containing the crystals of the present invention or the composition of the present invention to the seeds or vegetative reproductive organs by the method of seed treatment described above. can be obtained

The crystal of the present invention or the composition of the present invention can be used as a control agent for plant diseases in agricultural lands such as fields, paddy fields, lawns and orchards. As plants, the following are mentioned, for example.

Corn, rice, wheat, barley, rye, soft wheat, sorghum, cotton, soybean, peanut, buckwheat, sugar beet, rapeseed, sunflower, sugar cane, tobacco, eggplant and vegetables (eggplant, tomato, bell pepper, red pepper, potato, etc.), Gourd vegetables (cucumber, pumpkin, zucchini, watermelon, melon, etc.), cruciferous vegetables (radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, kale, broccoli, cauliflower, etc.), Asteraceae vegetables (burdock, mustard radish, Artichoke, lettuce, etc.), lily vegetables (green onion, onion, garlic, asparagus, etc.), buttercup vegetable (carrot, parsley, celery, parsnip, etc.), coliaceae vegetable (spinach, chard, etc.), Lamiaceae vegetable (perilla, mint, basil, etc.), strawberry, sweet potato, yam, taro, caustic fruits (apple, pear, Japanese pear, quince, quince, etc.), nuclear fruit (peach, plum, nectarine, plum, cherry, apricot, prune, etc.) , Citrus fruits (Wenzhou citrus, orange, lemon, lime, grapefruit, etc.), nuts (chestnut, walnut, hazelnut, almond, pistachio, cashew nut, macadamia nut, etc.), fruit fruits (blueberry, cranberry, blackberry, raspberry, etc.) etc.), grapes, persimmons, olives, loquats, bananas, coffee, date palms, coco palms, tea, mulberry, ornamental plants, forest plants, grasses, grasses.

The plant also includes genetically modified crops.

Example

Hereinafter, the present invention will be described in more detail by showing production examples, reference production examples, formulation examples, and test examples, but the present invention is not limited to these examples. In addition, "%" and "part" in an Example mean "weight%" and "part by weight" unless otherwise indicated.

Moreover, about the produced crystal|crystallization of this invention, various physical properties were measured using the apparatus (measurement conditions are attached) as follows.

Powder XRD

Powder X-ray diffraction device: SmartLab (manufactured by Rigaku Co., Ltd.)

X-ray output: Cu-Kα, 45 kV, 200 mA

Sampling width: 0.02°

Scanning range: 2° ∼ 50°

Measurement temperature: room temperature

single crystal XRD

(Ra1 form crystal)

Device: R-AXIS RAPID (manufactured by Rigaku Co., Ltd.)

X-ray source: Mo-Kα

Measurement temperature: room temperature

Solve: SHELXT

Refinement: SHELXL

(Ra2 form crystal)

Device: R-AXIS RAPID (manufactured by Rigaku Co., Ltd.)

X-ray source: Mo-Kα

Measurement temperature: room temperature

Solve : SIR2014

Refinement: SHELXL

(Ra3 form crystal)

Device: XtaLAB Synergy (manufactured by Rigaku Co., Ltd.)

X-ray source: Cu-Kα

Measuring temperature: 100 K

Solve: SHELXT

Refinement: SHELXL

DSC

Device: DSC Q2000 (manufactured by TA instruments)

Temperature increase rate: 2 ℃/min

Sample amount: 0.5 ∼ 5 mg

Measuring atmosphere: nitrogen

Fourier Transform Infrared Spectroscopy (FT-IR)

Device: Nicolet iS50 (manufactured by Thermo Fisher Scientific Inc.)

Measurement method: diamond ATR method

Brown Rice Raman Spectroscopy

Apparatus: NRS-5100 (manufactured by Japan Spectroscopy)

Laser Wavelength: 532 nm

light microscope

Light microscope: Leica Z16 APO (manufactured by Leica Microsystems)

Camera: Leica MC170 HD (manufactured by Leica Microsystems)

Magnification: 115x

An example of the preparation of the crystal of the present invention is described.

Preparation Example 1

(Preparation of Ra2 type crystal)

30 mg of Compound A was dissolved in methanol at 60°C to prepare so as to be 375 mg/mL. After cooling this solution to room temperature, it was irradiated with a laser under the following conditions, and it left still at 20 degreeC after that, and Ra2-type crystal|crystallization was obtained.

The laser irradiation conditions were as follows.

<Femtosecond laser>

Wavelength: 800 nm

Pulse width: 181 fs

Number of pulses: 125 pulses/10 seconds

Preparation 2

(Preparation of Ra1 crystal)

200 mg of the Ra2 form crystal obtained in Production Example 1 was weighed into a 20 mL capacity sample bottle, and heated at 130°C for 2 hours to obtain an Ra1 form crystal.

Preparation 3

(Preparation of Ra3-type crystal)

To 100 mg of the Ra1 crystal obtained in Production Example 2, 1 mL of diisopropyl ether was added, and the suspension was heated to 60° C. and stirred at 1000 rpm for 2 days, after which the solvent was removed to obtain an Ra3 crystal. .

Reference Preparation Example 1

(Preparation of Ra4 type crystal)

The Ra4 crystal was prepared by dissolving Compound A in toluene and recrystallizing it according to the method described in WO 92/12970 (Patent Document 1).

The physical property data of the crystal|crystallization of this invention are shown below.

Ra1-type crystals

IR characteristic peaks: 2933.0, 1648.4, 1632.0, 1606.6, 1554.6, 1338.8, 1082.9, and 1036.5 cm ^-1 .

Raman characteristic peaks: 2946, 2927, 2858, 1649, 1631, and peaks in the vicinity of 1397 cm ^-1 .

XRD characteristic peaks:

Table 1 shows, but not limited to, diffraction peak values as a diffraction angle (2θ±0.2°) for characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 1 .

Table 1

Typical diffraction peak values include, for example, 7.1 ± 0.2, 8.6 ± 0.2, 8.9 ± 0.2, 9.1 ± 0.2, 13.3 ± 0.2, 14.0 ± 0.2, 14.3 ± 0.2, 14.8 ± 0.2, 16.0 ± shown in Table 1 0.2, and 16.4 ± 0.2.

Ra2-type crystals

IR characteristic peaks: 3292.4, 2957.1, 2927.5, 1659.1, 1642.0, 1544.1, 1133.5, and 1123.2 cm ^-1 .

Raman characteristic peaks: peaks around 3118, 2924, 2876, 1658, and 1641 cm ^-1 .

XRD characteristic peaks:

Table 2 shows, but not limited to, diffraction peak values as a diffraction angle (2θ±0.2°) for characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 2 .

Table 2

Typical diffraction peak values include, for example, 4.3±0.2, 8.5±0.2, 10.8±0.2, 11.4±0.2, 12.4±0.2, 12.8±0.2, 15.1±0.2, 16.1±0.2, 16.8 shown in Table 2 above. ± 0.2, and 19.1 ± 0.2.

Ra3-form crystals

IR characteristic peaks: 3301.7, 2959.1, 2858.1, 1654.4, 1644.3, 1545.6, 1518.3, 1133.9, 1123.3, and 1032.8 cm ^-1 .

Raman characteristic peaks: peaks in the vicinity of 3046, 2928, 1652, 1588, and 1545 cm ^-1 .

XRD characteristic peaks:

Table 3 shows the diffraction peak values as a diffraction angle (2θ±0.2°) for the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 3 , but is not limited thereto.

Table 3

Typical diffraction peak values include, for example, 3.6 ± 0.2, 7.1 ± 0.2, 7.4 ± 0.2, 9.6 ± 0.2, 11.9 ± 0.2, 12.5 ± 0.2, 12.9 ± 0.2, 14.3 ± 0.2, 15.7 ± shown in Table 3 0.2, and 17.9 ± 0.2.

For comparison with the Ra1-type crystal, the Ra2-type crystal, and the Ra3-type crystal of the present invention, various spectral values of the Ra4-type crystal are shown below.

Ra4 form crystals

IR characteristic peaks: 2953.8, 1635.5, 1608.7, 1553.2, 1138.7, 1066.8, 1034.2, and 1012.3 cm ^-1 .

Raman characteristic peaks: peaks around 2928, 2859, 1491, 1398, and 1311 cm ^-1 .

XRD characteristic peak

Table 4 shows the diffraction peak values as a diffraction angle (2θ±0.2°) for the characteristic diffraction peaks in the powder X-ray diffraction pattern shown in FIG. 4 , but is not limited thereto.

Table 4

Typical diffraction peak values include, for example, 5.8 ± 0.2, 7.2 ± 0.2, 8.6 ± 0.2, 13.8 ± 0.2, 16.3 ± 0.2, 16.7 ± 0.2, 17.4 ± 0.2, 17.7 ± 0.2, 19.5 ± shown in Table 4 0.2, 19.8 ± 0.2 and 20.7 ± 0.2.

For crystals of the present invention, crystallographic data of single crystals are shown in Table 5 below.

Table 5

The control effect of the crystals of the present invention against plant diseases was measured by the following test examples.

Test Example 1

5 parts of Ra1 crystals or Ra4 crystals as a comparison object, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1:1), and 60 parts of water are mixed, and finely pulverized by wet grinding By doing so, a formulation was obtained. To this formulation, water was added so that the concentration of Ra1 crystals or Ra4 crystals was 2 ppm to obtain a diluted solution.

The plastic pot was filled with soil, soybeans (variety: Heukchunseok) were sown there, and it was grown for 15 days in a greenhouse. Thereafter, an aqueous suspension of soybean rust (Phakopsora pachyrhizi) spores was spray-inoculated. After inoculation, it was left overnight at 23° C. under high humidity, and after culturing for an additional 3 days in a greenhouse, the diluted solution was applied to leaves to sufficiently adhere to the leaf surface of the soybean. After spraying, the plants were air-dried, and only at night was placed under high humidity, and the lesion area was investigated 7 days after spraying (lesion area of the treatment group).

On the other hand, in the untreated group, the same operation as in the treated group was performed except that Ra1 crystals or Ra4 crystals were not treated, and the area of soybean rust lesions in the untreated group was investigated (lesion area of the untreated group).

From the lesion area of each treated group and untreated group, the effect of the treated group was calculated by the following "Equation 1".

The results are shown in Table 6.

「Formula 1」

Efficacy (%) = [1 - (lesion area in treated group / lesion area in untreated group)] x 100

Table 6

It was found that the Ra1 crystal exhibits a higher potency than that of the Ra4 crystal.

Test Example 2

5 parts of Ra2 type crystals, Ra3 type crystals, or Ra4 type crystals as a comparison object, 35 parts of a mixture of white carbon and polyoxyethylene alkyl ether sulfate ammonium salt (weight ratio 1:1) and 60 parts of water are mixed, and wet pulverized A formulation was obtained by fine pulverizing by the method. To this formulation, water was added to obtain a diluted solution such that the amount of Ra2 crystal, Ra3 crystal, or Ra4 crystal was 50 ppm.

The plastic pot was filled with soil, and rice (cultivar: Hinohikari) was sown there, and it was grown for 17 days in a greenhouse. The diluted solution was applied to leaves so as to sufficiently adhere to the leaf surface of the rice. After spraying, the plants were air-dried and cultivated outdoors for 8 days. After that, in a greenhouse at 24 ° C during the day and at 20 ° C at night, under high humidity, the spread-treated rice and rice seedlings infected with Pyricularia oryzae were placed in contact with them for 11 days, and then the lesion area was investigated (lesions in the treatment group). area).

On the other hand, in the untreated group, the same operation as in the treated group was performed except that Ra2 crystal, Ra3 crystal, or Ra4 crystal was not treated, and the rice blast lesion area in the untreated zone was investigated (lesion area of the untreated group).

From the lesion area of each treated group and untreated group, the efficacy of the treated group was calculated by the above "Equation 1".

The results are shown in Table 7.

Table 7

It was found that the Ra2 type crystal and the Ra3 type crystal exhibit higher potency compared with the Ra4 type crystal.

Crystals of the present invention (Ra1 type crystals, Ra2 type crystals, and Ra3 type crystals) exhibit an excellent control effect against plant diseases.

Claims (9)

3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide In
2θ = 7.1 ± 0.2 °, 8.6 ± 0.2 °, 8.9 ± 0.2 °, 9.1 ± 0.2 °, 13.3 ± 0.2 °, 14.0 ± 0.2 °, 14.3 ± 0.2 ° in powder X-ray diffraction by Cu-Kα ray Form Ra1 crystals having diffraction peaks at 14.8 ± 0.2°, 16.0 ± 0.2°, 16.4 ± 0.2°, 20.3 ± 0.2°, and 20.6 ± 0.2°;
2θ = 4.3 ± 0.2 °, 8.5 ± 0.2 °, 10.8 ± 0.2 °, 11.4 ± 0.2 °, 12.4 ± 0.2 °, 12.8 ± 0.2 °, 15.1 ± 0.2 ° in powder X-ray diffraction by Cu-Kα ray Form Ra2 crystals having diffraction peaks at 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2°, and
2θ = 3.6 ± 0.2 °, 7.1 ± 0.2 °, 7.4 ± 0.2 °, 9.6 ± 0.2 °, 11.9 ± 0.2 °, 12.5 ± 0.2 °, 12.9 ± 0.2 ° in powder X-ray diffraction by Cu-Kα ray Ra3-form crystals with diffraction peaks at 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2°
At least one crystal selected from the group consisting of. 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole according to claim 1 In -4-carboxamide, 2θ = 7.1 ± 0.2 °, 8.6 ± 0.2 °, 8.9 ± 0.2 °, 9.1 ± 0.2 °, 13.3 ± 0.2 °, 14.0 in powder X-ray diffraction by Cu-Kα ray Form Ra1 crystals with diffraction peaks at ± 0.2 °, 14.3 ± 0.2 °, 14.8 ± 0.2 °, 16.0 ± 0.2 °, 16.4 ± 0.2 °, 20.3 ± 0.2 °, and 20.6 ± 0.2 °. 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole according to claim 1 In -4-carboxamide, 2θ = 4.3 ± 0.2 °, 8.5 ± 0.2 °, 10.8 ± 0.2 °, 11.4 ± 0.2 °, 12.4 ± 0.2 °, 12.8 in powder X-ray diffraction by Cu-Kα ray Form Ra2 crystals with diffraction peaks at ± 0.2°, 15.1 ± 0.2°, 16.1 ± 0.2°, 16.8 ± 0.2°, and 19.1 ± 0.2°. 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole according to claim 1 In -4-carboxamide, 2θ = 3.6 ± 0.2 °, 7.1 ± 0.2 °, 7.4 ± 0.2 °, 9.6 ± 0.2 °, 11.9 ± 0.2 °, 12.5 in powder X-ray diffraction by Cu-Kα ray Form Ra3 crystals with diffraction peaks at ± 0.2°, 12.9 ± 0.2°, 14.3 ± 0.2°, 15.7 ± 0.2°, and 17.9 ± 0.2°. A plant disease control composition comprising one or more crystals according to any one of claims 1 to 4. A method for controlling a plant disease, comprising treating a plant or soil in which the plant grows with an effective amount of one or more crystals according to any one of claims 1 to 4. Use of one or more crystals according to any one of claims 1 to 4 for controlling plant diseases. A composition comprising at least one component selected from the group consisting of group (a), group (b), group (c) and group (d), and at least one crystal according to any one of claims 1 to 4 :
Group (a): the group consisting of insecticidal active ingredients, acaricide active ingredients and nematicidal active ingredients;
Group (b): bactericidal active ingredients;
Group (c): plant growth modulating components;
Group (d): repellent components. A seed or vegetative reproductive organ containing an effective amount of one or more crystals according to any one of claims 1 to 4 or an effective amount of the composition according to claim 7.

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